Aqueous, solid particle dispersions of dichalcogenides for photographic emulsions and coatings

Abstract

This invention provides a method of preparing a silver halide photographic emulsion which comprises adding to the silver halide emulsion a solid particle dispersion of a non-labile chalcogen compound represented by Formula I: R.sup.1 --X.sup.1 --X.sup.2 --R.sup.2 (Formula I) It further provides a silver halide photographic emulsion prepared by the above method.

What is claimed is: 
     
       1. A method of making a photographic silver halide emulsion comprising precipitating and sensitizing a silver halide emulsion and further comprising adding to the silver halide emulsion an antifogging amount of a non-labile chalcogen compound represented by Formula I:   R.sup.1 --X.sup.1 --X.sup.2 --R.sup.2                      (Formula I)     where X 1  and X 2  are independently S, Se, or Te; and R 1  and R 2 , together with X 1  and X 2 , form a ring system, or are independently substituted or unsubstituted cyclic, acyclic or heterocyclic groups; and   wherein the dichalcogenic compound is added as a solid particle dispersion.   
     
     
       2. The method of claim 1 wherein R 1  and R 2  are independently substituted alkyl or aryl groups; the dichalcogenide molecule is symmetrical and the molecular weight is greater than 210 g/mol. 
     
     
       3. The method of claim 1 wherein the dichalcogenide compound is a disulfide compound represented by Formula II or III: ##STR9## where G is independently in an ortho, meta, or para position on the aromatic nucleus relative to the sulfur and is hydrogen, hydroxy, SO 3  M or NR 3  R 4  ; M is hydrogen, or an alkaline earth, alkylammonium or arylammonium cation;   R 3  is hydrogen, or a substituted or unsubstituted alkyl or aryl group;   R 4  is hydrogen, O═C--R 5 , or O═C--N--R 6  R 7  ; and   R 5 , R 6 , and R 7  are independently hydrogen, or hydroxy, or an unsubstituted alkyl, or aryl group, or a substituted or unsubstituted fluoroalkyl, fluoroaryl, carboxyalkyl, carboxyaryl, alkylthioether, arylthioether, sulfoalkyl, or sulfoaryl group or the free acid, alkaline earth salt or alkylammonium or arylammonium salt of the aforementioned groups; ##STR10##  where Z contains substituted or unsubstituted carbon or hetero atoms sufficient to form a ring; and R 8  is a substituted or unsubstituted alkyl or aryl group of 2 to 10 carbon atoms, or the free acid, alkaline earth salt, arylammonium or alkylammonium salt of the aforementioned groups.   
     
     
       4. The method of claim 3 wherein the disulfide is represented by Formula II and the molecule is symmetrical; and where G is in an ortho, meta, or para position on the aromatic nucleus relative to the sulfur and is NR 3  R 4  ; and R 4  is hydrogen, or O═C--R 5 . 
     
     
       5. The method of claim 4 wherein G is in a para position relative to sulfur, R 3  is hydrogen or methyl, R 4  is O═C--R 5  and R 5  is an alkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 10 carbon atoms or a trifluoromethyl group. 
     
     
       6. The method of claim 5 wherein the disulfide compound is bis (4-acetamidophenyl) disulfide. 
     
     
       7. The method of claim 3 wherein the disulfide compound is represented by Formula III and R 8  is a substituted or unsubstituted carboxyalkyl, carboxyaryl, alkyl ester, or aryl ester group of 2 to 10 carbon atoms, or the free acid, alkaline earth salt, arylammonium or alkylammonium salt of the aforementioned groups. 
     
     
       8. The method of claim 7 wherein Z comprises carbon atoms sufficient to form a ring and R 8  is a substituted or unsubstituted alkyl or aryl group of 4 to 8 carbon atoms, or the free acid, alkaline earth salt, arylammonium or alkylammonium salt of the aforementioned groups. 
     
     
       9. The method of claim 8 wherein R 8  is a substituted or unsubstituted carboxyalkyl, carboxyaryl, alkyl ester, or aryl ester group of 4 to 8 carbon atoms, or the free acid, alkaline earth salt, arylammonium or alkylammonium salt of the aforementioned groups. 
     
     
       10. The method of claim 9 wherein the disulfide compound is 5-thioctic acid. 
     
     
       11. The method of claim 3 wherein the antifogging amount of the disulfide compound is 1×10 -7  to 1×10 -2  mol/mol Ag. 
     
     
       12. The method of claim 3 wherein the antifogging amount of the disulfide compound is 1×10 -5  to 3×10 -4  mol/mol Ag. 
     
     
       13. The method of claim 3 wherein the solid particle size is less than 1 micron. 
     
     
       14. The method of claim 3 wherein the solid particle dispersion is a solid particle gelatin dispersion prepared by mixing the disulfide compound with a surfactant, an aqueous phase and a milling media to form a slurry; milling the slurry; filtering out the milling media; and mixing the remaining slurry with gelatin. 
     
     
       15. The method of claim 14 wherein the surfactant is an alkylated aryl polyether sulfonate. 
     
     
       16. The method of claim 3 wherein the silver halide emulsion is a silver bromoiodide emulsion. 
     
     
       17. A method of making a photographic silver halide emulsion comprising precipitating and sensitizing a silver bromoiodide emulsion and further comprising adding to the silver bromoidide emulsion 1×10 -7  to 1×10 -2  mol/mol Ag of a disulfide compound represented by formula II; ##STR11## wherein G is in a para position relative to sulfur and is NR3R4, R 3  is hydrogen or methyl, R 4  is O═C--R 5  and R 5  is an alkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 10 carbon atoms or a trifluoromethyl group; and wherein the disulfide compound is added as a solid particle gel dispersion.   
     
     
       18. The method of claim 17 wherein the antifogging amount of the disulfide compound is 1×10 -5  to 3×10 -4  mol/mol Ag. 
     
     
       19. The method of claim 17 wherein the solid particle size is less than 1 micron. 
     
     
       20. The method of claim 17 wherein the solid particle gel dispersion was prepared using an alkylated aryl polyether sulfonate as a surfactant. 
     
     
       21. A photographic silver halide emulsion prepared by the method described in any one of claims 1 through 20.